An efficient and environmentally friendly synthetic protocol has been presented to synthesize α‐aminonitriles from aldehydes, amines and trimethylsilyl cyanide using 10 mol% iron(III) tosylate hexahydrate (Fe(OTs)3 ⋅ 6H2O) as a green catalyst in aqueous media through one‐pot procedure. Iron(III) tosylate hexahydrate is a promising catalyst, introduced first time for the synthesis of α‐aminonitriles in aqueous media as it is commercially available, inexpensive, non‐toxic, operational simplicity and has a short reaction time with excellent yields is awaited to contribute to the development of novel green protocol for the synthesize α‐aminonitriles.